Method of refining liquid hydrocarbons



E. B. MsLLx-:R ET AL,

Filed June 1v. 1951 METHQD OF REFINING LIQUID HYDROCARBONS Nov, l,1932..

Iications.

PatetedNozv. l, v1932 l A .UNiran STATES; E

o. 'oo NNoLLY, or DALTIMOBEMARYLAD, AissIG ons i animar 11.- MILLED ANDGERALD yoiij MARYLAND To THE sILIoa GEL c onroaATIon, or BALTIMORE, A'VooitnAr'I No Application medium 17, 1931,' serial No'. 545,099, 'and 1nnuisianafqn a 192s,

The present invention-relates av method of refining-liquid hydrocarbons,for example, *petroleum oils s'uch as gasoline, kerosene, and

oils obtained by distillation of coal and the like, of the nature ofbenzol etc. v f A f Liquid hydrocarbons *are refined' to meetcertain'trade specifications as to sulphur content, color, odor, acidcontent, sweetness, cor-.. rosion, 'and gums. 1

vSome liquid hydrocarbons can be refined to the required specificationswith a relative-- 1y small quantity of porous adsorbent like silicagel.- /Others requlre a large quantity of the porous adsorbent, say onepart of adsorbent to one part of the hydrocarbon, in order to meet thespeoiications. Still other hydrocarbons,` if treated with an adsorbentlike sill ical gel alone, cannot be made to satisfy all' thespecifications.

flhe principal object of the present inven-` tion is to provide a methodof refining liquid hydrocarbons so that they will comply with any andall of the usual specifications and accomplishing this result with ahigh ratio of the hydrocarbon to the porous adsorbent employe Someliquid hydrocarbons, before refinin comply with one or more of theusualspeci- The treatment accordin present 'invention may. vary yin.accordance with what specifications are to be met.. vFor the purpose ofthe resent case, the treat-y ne'nts may be divide into four classes asfol- 1. To remove elemental'sulp ur only.

2. To Y meet the doctor t vtI only (make sweet.

3. o meet all the specifications except-the gum test. L 4. To removegum'forming meet'all the other specifications.-

1' The treatmentof the first class mentioned above, that is to say,where? it is desired to remov'c the elementalsulphur only, consistsinltreating the liquid hydrocarbon w1th a solid, porous adsorbent likesilica gelaat an' METHOD oF` :termine LIQUID nYDnocAn'noNs the one for-perature and with the" formin constituentsftheprocess onsist :the sluge removed fpriorato treatment. -T he treatment with y -sults, theadsorbent should also. nated with one or more me tallicoxides.I The?,

constituents from highly unsaturated hydrocarbons .and-

v.out the present-invention; and

25 to 100 partsorlmoreofgt y to one part'of the adsorbei depending upontheainon an the sulphur. For the secondzand t tioned above, that is "fto meet any of theo en k man.prac@v4 ing'the hy rocarbon' `vvith arsolsorbent like silica` geljlimpre" e "60 or more metallic oxidesatl nquidphase. The ratjiapfgh carbon tothel adsorbent'in l`b th i for the firstclass. ,1; For the fourth class''th saturated hydrocarbfoiis` con lpg?in treatinv the hydrocarbon with ous adsoient, like silica gel, ,i with4al polymerizing agenty-su quant-ity of strong acid, vandthen d treatedliquid. Y Preferabl how small quantity of'a'cidv isfa ded to. th ,a fmed1i uidinstead Oftto thef-,edprbe l ead is effected at elevatedgtemperatrecel/id the hydrocarbon' ing, thefzg` 1 1 Whether the agent is addedtolthega orbe;1t,'l or the agent and adsorbenttreatme fectedsuccessively, in s omegcases erregratio of the hydrocarbonato ythesolid-porous adsorbent may be about the same as vfor `,the

other classes. t Other objects and features of novelt Y v y, `beapparent' from the descriptiontakemin; connection with the drawing inwhich: L l y u' Figurel is a diagrammatlc elevationlwithA parts insection of an apparatus .for carrying Figure2 a diagrammaticillustration of y apparatus'used in conjunction with thegapparatus^ ofFigure 1. when it isdesired/togive y the partiallyreined hydrocarbon asecond treatment with adsorbent, abnormal temperature. .Y l f l Theapparatus illustrated in thedravsri'ng'v ing thoroughly agitated bymeans of the rotating agitator 4.

The polymerizing ag'ent may be an acid, an organic material such asdi-methyl sulphate, or saltssuch as anhydrous aluminum chloride. Usuallythe mostI economical agent is sulphuric acid. This is employed in aquantit-y varying from .1% to .5% of the oil, where strong acid, thatis, 80% to 100% strength, is used. e l

The agent, such as acid, is employed in a f relatively small quantityand 4reacts with a portion only ofthe unsaturated constituents of theoil to form reaction products including which are in solution in thehydrocarbon. Later in the (process, the hydrocarbon is treated with an asorbent, and it is thought that some'or all of theseums, in solution inthe liquid, are 'adsorbe by the adsorbent and/or deposited thereon, andact catalytically to polymerize the balance of the gum forminconstituents in the hydrocarbon. e he treated oil is discharged from thetank i 1 through throughpipe 5 connected to a series of settling tanks 6arranged in arallel. In addition to polymerizing gum ormingconstituents, the polymeri'zlng agent also throws out a small quantityof sludge, and this settles out in the settling tanks '6 and ma in thebottom thereof.

After the sludge has been permitted to settle to the bottom of the tank,the hydrocarbon is discharged through pipe 8 into pipe 9 lead-l ing topump 26. It wi be understood that the treated oil discharged through thepipe 9 contains the acid hydrocarbon reaction products, such as theolymerized gums, in solution. Suitable val) the pipes so that the acidtreatment tank can be put in communication with any one of the settlingtanks and any one of the'settling tanks -cari-be ut in communicationwith the pump 26 lea mg to the adsorbent treatment apparatus hereinafterdescribed.

The series of settling tanks '6 permits a substantially continuous .flowof partially purified oil.A Obviously, any number of settling tanks maybe employed.

The adsorbent treatment. apparatus includes a storage ho per 10 for theadsorbent material and a suita le means such as a worm conveyor 11connected'so as to discharge into an agitator 12.

be drained through the valved outlets 7 ves are provided in each of Ifit is desired to: impregnate the adsorbent v with the polymerizing'agentrather than to add it directly to the oil, the agent, such assulphuric acid, may be introduced as a s ray at 12Il in an amount up toabout 5% "o the weight of the adsorbent, its strength being from 80% to100% where sulphuric acid is employed. It is to be understood, however,that it is preferred to introduce the acid directly into the oil in thetreatment tank 1.

In additionto the adsorbent, the agitator is supplied with suiiicienthydrocarbon liquid from pipe 14 leading from the filtrate pump 15, sothat the mixture will flow from the agitator through one of the valves16 or 17 to the percolator 18 or 19. About three parts of the liquid toone part of the adsorbent is suicient for this purpose. -v

Each of the percolators is provided with a `bottom screen 20 and a topscreen 21, and a steam jacket 22 having a steam inlet 23 and a steamoutlet 24, so that the contents of the percolator are maintained at anelevated temperature. The mixture of adsorbent and liquid just describediills the space between -screens 20 and 21, and this space is providedwith suitable agitators 25 carried by a shaft 25, which may be rotatedby any suitable means.

After the percolator has been charged with the adsorbent, the liquidl tobe refined is passed through the same. For this purpose a pump 26withdraws the liquid to be treated from one of the settling tanks 6, andthrough pipe 28 conducts it to a heat exchanger 29 then through a heater30 in which the liquid is heated, and then by a pipe 31 to the bottom ofthe percolator. Valves 32 and 33 control the supply of liquid to thepercolators. It

will be understood that when one of these valves is opened, the other isclosed so that one percolator only v'is used at a time. The liquid to berefined then passes upthrough one o f the percolators where it isbrought into contact with the adsorbent and refined.

Valves-32 and 33are interposed between the percolators 18 and 19 and thedischarge pipe 34:.4 These valves may serve either to totally disconnectthe respective percolators from the pipe 34, or to cut down the-rate ofdischarge of liquid into pipe 34, so that, if necessary, the pressure inthe rcolators may be raised, so as to maintain t e h drocarbon as aliquid at the tem erature o the treatment. The liquid disc arged fromthe percolators passes through pipe 34 tothe heat exchanger 29 wheresome of the heat of the partially refined liquid is transferred to theincoming untreated liquid. From Ithe heat exchanger, the partiallyrefined liquid passes to the distillation apparatus 13 where thehydrocarbon is distilled from the polymerized gums, the completelypurified oil being received in the tank 27.

Furthermore, by means of valves 36', the flow of liquidthrough thepercolators, ef'

er than by valves 32 and 33', as previously suggested. Valves 36 may beoperated auto# matically by the pressurein the percolators, whereas thevalves 32 and 33 would best be used only to cut any percolator in or outof the circuit as desired.

In any instance. it is desirable to keep the pressure inthe percolatorsjust high enough to maintain practically all the oil in the liquidstate. v

The acid treated oil is supplied to either percolator until about 25 to100 or more parts of oil to one part of the adsorbent How through thepercolator, the amount of oil that can be treated in one batch of theadsorbent depending upon the amount and nature of the impurities. Fromthe foregoing it is seen that the adsorbent is employed in a quantityinsuflicient to adsorb any `substantial amount ofthe reaction products',i. e. the polymerizcd gums in solution in the hydrocarbon, al' though itwill adsorb the liquid, elemental surphur` as explained hereinafter.

After the abovef'stated amount of liquid` has been treated in saypercolator 18, valves 32 and 32 are closed, and valves 33 and 33 ofpercolator 19 are openedv lso that the" oil is now passed through andtreated in the percolator 19. While the treatnent is going on in thesecond percolator, the vadsorbent in the first percolator is dischargedthrough pipe 38 into an agitator 39, and from this agitator by means ofpipe 40 toa filter 41 which may be of the vacuum type, the vacuum pumpbeing indicated atv42, and itsvdischarge pipe at 43. y. Preferably, thispipe discharges into the casing of the filter so as to return to thefilter any vapors. The suctionof the vac"uum pump is connectedl by pipe44- to a moisture trap 415 which in turn, by means df pipe 46, is connected to the vacuum receiver 417. Into this i receiver, the li uidfiltrate` irdm theilter Hows through p1pe48. The filtrate accumulatinginreceiver 47 Hows through pipe 49 to Hltrate lpump 15 previouslymentioned.

The adsorbent separated by the Hlter lis conveyed, asby a worm conveyor50,v to a primary activator'l whereinit is subjected to the heat fromvthe'hot gases from furnace 52. The products of combustion from thefurnace pass into Hue `53 wherein there is la damper 54which-controlsthe proportion of thesegass` that ass directly ltotheprimary activator `5 1, The gases that pass through the secondaryactivator How through Hue 53` to the primar activator, the'amount ofgases being control ed byfa damper 54a in Hue 53. The adsorbent passesfrom the.` primary activator to the secondary activator through 'confduit 51,a and `worm'conveyors 51"r and 51,.

- coveredl oil tank '66..k v

As stated, the hydrocarbon being treated before delivery to thepercor-The secondary activator is maintainedjat A'a higher temperature thanthel primaryh'acti'f vator. These activators preferablynarfo the ty ehaving a series of hearths superpo'sd ongeac other, there beingradialarms f in over each hearth to agitate and -feedt e a sorbentregenerate The Howl of gases in th induced by the draft fan 56. i 111]'g .From the Secondary activator" 255, generated adsorbent isconveyed-'-ash' conveyor 57,'to'a pipe 58'connected`toffa.. cyfy .cloneseparator 59l whereinthe" adsorbent is".A

-separatedfrom theair and Settlesjintdthe-{Q'L-fstorage hopper 10.,TheairI 'separated by the f cyclone separator,passesfthroughpipei() tof;a dust collector l-wherein'any particles'of (passing therethrough, andfes-? adsorbent that may be carried along in'lthe air are recovered. yThe How of the mixture .I 85.'

of air and adsorbent in the vpipe 58, separator 59, pipe-60, and, dustcollector (itis brought about by fan 62 at thexairfdischa'rge end 'ofthe dustcollector. n

An liquid hydrocarbon liberated from the adsor nt in the activators maypass through pipe 63 to thecondenser 64`where lit is con-A 2 densed 'andconducted may be heated lator.

` While being treated with the Aadsorbent i islmaintained ,at anelevated temperature of f from 150 to 500 F., preferably at about 300 to325"E 1".,*atwhich temperature any elemental sulphur present ywill be inthe' llquidv phase, so that the adsorbent may separate it from the` oilby.adsorption"in `its pores.;` Although it is preferred to maintain the-temperatures at about 300.'t'o 325 F., satisfactemperature at about250" to 300 Iig/o1;r even 240 F. The liqu'id'is maintainedv at this f lelevated temperature by means of thestearn in the steam jacket 18. v

Instead of separating the refined-'hydro'.-

carbon froin'the dissolved, reaction products los vtory results may beobtained'byhaving the by distillation, the same result may be eEectitemperature and/pressure; l v For this purpose, vthevprodu'ct from thepercolators 18 and 19 instead of being led to v. the distillationapparatus. 13 is lconducted throughpipe 34"'and cooler 35 to-an agitatoradsorbent by means such as a filter pressA 4.1l

ed by passing the vliquid with the dissolvedvv l' .p reaction productsthereinl througha porous4 .lisabsorbent material like silica gelat'normal j j v las or a Dorr thickner; or the like, apdthe'n di's-v 'icharged into the finished oil tank 37.

' 00 vapor and oxi If desired, the adsorbent, such as silica gel,employed in the agitator 19 may be impregnated with one or more of thesubsequently mentioned metallic oxides.

The preferred porous adsorbent material adapted `for use in the practiceof the present invention is silica gel. This material is a hard, solidsubstance having ultramicroscopic pores in such number that it willadsorb vapors and gases-at very W partial pressures. u This silica gelwill adsorb water vapor to such an extent as to contain at least 10% ofits own weight of water. when in equilibrium with water vapor at C. anda partial pressure of 22 mm. of mercury. The better grades d'2 willadsorb as high as 40% of water under these conditions.

When highly unsaturated hydrocarbons p containing gum formingconstituents such'as o often advantageous to employ an adsorbent havingassociated therewith one or more metallic oxides.

For impregnating the adsorbent material, fa metallic oxide is employedwhich has the property of readily combining with sulphur to form acompound which may be broken down by heat, such as the oxides of'copper, iron lead, zinc, antimony, and silver,` or any hnation thereof.The preferred adsorbent for carrying out the present invention is silicagel, of the nature hereinbefore descrlbed, impregnated with copper oxideor a combination of iron oxide and copper oxide, The maximum amount ofthe oxide employed is about one per cent of .the weight of the`adsorbent for each oxide. That is to say, where one oxide is employed, amaximum of about one per cent of this oxide is us'ed.

40 Where two oxides are used, 'each is present in the amount of amaximum of about one per cent.

Toillustrate a method of impregnating the .adsorbent material with anoxide, the process 0f impregnating silica gel with copper-oxide will bedescribed, although it will be apparent that such method may be used .incon- 'nection with other metals than copper and with other adsorbentmaterials. An aqueous solution of almost any easily decomposablesolublecopper salt, preferably cop er nitrate of anydesired strength isthoroug ly mixed with the gel by direct mixing or by a spray,

or in any other suitable mannen Copper nitrate readily breaks down underheat at a to 300 F'. to form the temperature of 200 green insolublebasic nitrate. The basic `ni trate, in turn', breaks down to forminsoluble copper oxide with the liberation of water des of nitrogen.'This forma; tion of copper oxide is complete at 1000 F. which is aboutthe highest 'temperature employed in theactivation of the adsorbent. .Ifthe gel is to be impregnated with an oxide 5 of one or more of the othermetals mentioned,

cracked gasoline and benzol are treated, it is 80% to 100%, the

use.

the procedure is the same, the salt that decomposes at the lowesttemperature being selected.

if the quantity of oil that one batch of adsorbent Will refine is 100%,the' acid may be added to the lirst 20%, thus forming gums some of whichdeposit on the adsorbent, and act catalytically, as explained above, topolymerize the remaining gum forming constituents inthe said 20% andalso the gum forming constituents in the remaining %of oil. The acid maybe sulphuric of any suitable concentration, for instance, 62 B., Vthequantity varyingfrom' 0.1% to 0.5% of the oil, as previously stated.

- Certain oils,particularly1 those containing suspended orl dissolvedwater, are more effectively purified if the acid or other agent be addedin two or more steps, the first addition serving topre--dry land thelater addition or additions to react with the impurities, includi-n thegums. The acid may be sulphuric o any desirable strength, for instance,qluantity varying within the limits above disc `posed.V K

As stated, the preferred adsorbent-mate-- rial is silica el, butbauxite, 'fullers earth, bentonite, car on, adsorbentclays, and-thelike, may be used, although they do not withstand the heat of activationas well as the gel and for this reason cannot be used over and over andare not adapted to commercial Insteadvof silica gel, other hard, porousgels might be used,such as tungstic, aluminio, stan-nic, etc. i

The apparatus has been described as emloyed for refining hydrocarbonshaving Irum orming constituents, to meet all the tradespeci-ications.Where there are no gum forming constituents in the liquidto be treated, the apparatus is used in the same way except that no acidis added to the adsorbent or unrened liquid, and the final distillationor adsorbent step is omitted.

Where the object of the reiining is to remove elemental sulphur, anunimpregnated l scribed is not in anyway to ofthe appended claims.

This application'is'a continuation in art of a plications Serial Number65,466, ed October 28,`1925, Serial Number 276,163, filed May 8,1928,andSerial Number 381,256, vfiled July- 26,-1929.1

vingthusdescribed the invention, what isiclairne'd -as-newand 'desiredto be secured byl Letters "Patent `is 2.v v i 1.,(ThcV methodofrefiningliquid hydrocarbons' containing forrnin ,jcon'stltuentscomprising, treating the hy roc'arbonlwith strong sulphuric acid of 80to100% strength in a quantity of 0.1 to

0.5% of thew'eight of the ,hydrocarbon in a series ofste'ps, settiingout and removing the resulting 1sludge, contacting said treatedhydrocarbon AWhile containing in solution acid-,hydrocarbonrea from saidacid treatment, with solid, porous,

adsorbent material ina quantity of less than 4% of the hydrocarbon at anelevated temperature-of from1150.d to 500 F. with the hydrocarbon.' inthe liquid phase, said material having copper and iron voxidesassociated therewith ina quantity of about 1% each of( the weight ot thematerial, Vseparating the hydrocarbon r'omtheadsorbent and distilling toseparate the hydrocarbon from the reaction' products andother impuritiesycon-- tained therein.

2.- Themethodoffreining liquid hydrocarbonsfcontaining unsaturatesincluding gum forming constituents comprising, treating 'the hydrocarbonwith j strong sulphuric acid of Sfljto y100% strength in a quantity of0.1 to 0.5%fothe 'Weightfoi the hydrocarbon in a series ots'teps`,settling' outand removing the resulting sludge,l @contactingsaid treated Hhydr ocarb'on Whilecontaining in. solution trig outfallu'"action""productsLresulting `from Y said acid marea@redacta nu"tained"therein:A

acid? )idrocarburi-reaction products resulting from Saidacidftre'atment, VWith solid, porous, adsorbent ,niaterialfinf vaquantity less than 4%"foi theliydrocarbon atan elevatedteinhydrfoca'rhrn4 r thejliquid phase, separating thehydrocarbon'jfromthe. adsorbent and distillingt separatetliehydroca'rbon from the other impurities con- 3. The method ofrefining yliquid hydrocarbons `'`ningnnsaturates"including gumconstituents comprising, treating n oearhoniwith strong'sulphuric acid"or to'100% strength'in a quantity of 0.1 to 0.5% of Ithe weight `of thehydrocarbon, setd 'removing the resulting sludge, contacting aidtreated'hydrocarbon While .containing solution acid-hydrocarbonretreatinent, withsilica `gel in af quantity less than; i%'fof,thefhydljocarbon. at an elevated temperatnieof from-'150 m500" F.with the renner-111911.@their?? Para lStarting the scope unsaturatesincludmg guml c tion lproducts resulting ing gu'm vforming constituentscomprising,

treating the hydrocarbon with strong su phuric acid inl a quantitsuflicient to polymerize a portion only o gum formin constituents,settling out and removing t e reand other'impurities coni sultingsludge, `contacting said treated hydrocarbon while 'containing insolution acidhydrocarbon reactionproducts resulting f rom said acidtreatment, with solid, porous, adsorbent material in a quantity-lessthan 4% of the hydrocarbon at an elevated tema perature of from 150 .to500 F., with the hydrocarbon in the liquid phase, separating thehydrocarbon from the adsorbent and distilling to separate thehydrocarbon from the reaction products and other impurities con-- tainedtherein. i

5. The method of refining liquid hydrocarbons containing unsaturatesincluding gum forming constituents comprising, treating'the hydrocarbonWith strong sulphuric acid in a uantity sucient to polymerize a portionon y of gum forming constituents, contacting said treated hydrocarbonWhile containing ,in solution acid-hydrocarbon reaction productsresulting from said acid treatment, with solid, porous, adsorbentmaterial, in a quantity less than 4% out the hydrocarbon at an elevatedtemperature of from 150 to 500 F., with the hydrocarbon in the liquidphase, separatin the hydrocarbon from the adsorbent an distilling Vtoseparate lthe hydrocarbon from the reaction products and otherimpurities contained therein.

to polymerize a portion only of gum forming constituents, contactingsaid treated hydrocarbon while containing in solution ac idhydrocarhonreaction products,V resulting from said acid treatment, with solid,porous,

adsorbent material in a quantity less than i% or" the h droc'arbonat anelevated ternperature with the hydrocarbon in the liquid phase,separating the hydrocarbon troni the adsorbent and distilling toseparate the hy drocarbon from the reaction products and .otherimpurities contained therein.

7. rlhe method of refining liquid hydrocarbons containing unsaturatesincluding m forming constituents comprising, treating the hydrocarbonwith strong sulphuric acid of 80 to 100% strength in a quantitysuil'lcient to polymerize a portion only of gum forming constituents,contacting said treated bons containing 5 temperature with thehydrocarbon in the liquidY phase, and distilling to separate thehydrocarbon from the reaction products and other impuritiescontained'therein..

8. The method of refining liquid hydrocarbons cozntainin unsaturatesincluding gum formingrosczonstituents comprising, treating the hy arbonwith strong sulphuric acid of 80 to 100% strength in a quantltysullicient Yto polymerize a portion only of gum forming constituents,contacting said treated hydrocarbonA while containing in solutionacidhydrocarbon products resulting from said acid treatment, with aporous adsorbent at an elevated temperature with the hydrocarbon in theliquid phase, and to separate the hydrocarbon from the reaction productsand other impurities contained thereln.

9. The method of reiining liquid hydrocarforming constituentscomprising, treating the hydrocarbon with strong sulphuric acid of 80 to100% in a quantity 'suilicient 'to polymerize a portion only ofgumforming constituents, consaid treated hydrocarbon while containing insolution acid-hydrocarbon reaction products rcsultingrom said'acidtreatment, with a rous adsorbent in a `quantity less than 4 o of thehydrocarbon at an elevated 3;"t mperature with the hydrocarbon in theliquid phase, and distilling to separate the hydrocarbon from thereaction products and other impurities contained therein.

- 10. The method of refining liquid hydro- 40 "carbpns such as crackedhydrocarbons containing gum forming constituents comprising, treatingthe hydrocarbon with strong sulphuric acid of 80 to 100% strength in aquantity of 0.1 to 0.5% of theweight of the 4 '51 hydrocarbon,contacting said treated hydrocarbon while containing in solutionFacidhydrocarbon products resulting from said acid treatment, with silicagel in'alua'ntity less than 4% of the hydrocarbon atan ele- `vatedtemperature under pressure suicient tormaintam the 'hydrocarbon` in theli uid phase, and distilling tosepara the hy rocarbon from the reactionproducts and other impurities contained therein.

11'. The method of refining liquid hydrocarbons such -as crackedhydrocarbons containing gum forming constituents comprisin treating thehydrocarbon with strong su huric acid, removing the resulting slu ge,contacting said treated hydrocarbon containing gums and gum-formingconstituents with porous adsorbent having associated therewith at leastone metallic oxide capable of readily combining with sulphur at an `elevated .temperature 1n the liquid phase, and

'separating 'the h at least 150 F. under maintain the hydrocarbon in`the liquid tpl jV4 drocarbon from the reaction products an otherimpurities contained therein. i Y

12. The method of re liquid hydrocarbons such as cracked `'hy 'ocarbonscontaining gum formin constituents compris'- isl, treatingA the hy huricacid, slu ge, contacting said treated hydrocarbon containing, gums andgum-forming constituents with a porousadsorbent at an elevated tem theydrocarbon from the reaction products and other impurities containedtherein.

13. The 'method of refining liquid hydrocarbons such as crackedhydrocarbons, comhydrocarbo n with af q `Wg'lllr p treating said suitabereagent in `suc polymerize a portion onl` of F n forming constituents insaid hydiyoca.v in contacting'said treated hydrocarbon a hard porous atan elevated temperature and separating the lgdrotarbon from e reactionproducts an tained therein.

rbon with strongA removing the resulting` re in the liquid phase,separating' preure Vsufcient tov other. impurities con- 14. The methodof refining light` iiyamcarbons, comprising treating said hydrocar' bonwith a suitable reagent 1n such quantity as will polymerize aportion'onl of form' constituents 1n said hy oca n, contacting saidtreated hydrocarbon with silica gel at an elevated temperature of atleast F. in the li uid phase and separating the hydrocarbon om thereaction products and other im urities contained therein. 15. The meth'of refining liquid hydroq carbons comp treating the hydrocarbon with vasuitab e reagent in anY amount suicient to pol'ymerize a portion only ofgum forming constituents, treatin the hydi'ocarbon containing polreaction products in solution with a porous adsorbent material havingassociated therewith at least one metallic oxide capable of readilycombining with sulphur said latter treatment accomplishingpolymerzationof remaining gum-forming constituents and then separatmg the hydrocarbonfrom the impurities and resulting reaction products.

vis effected vat an elevated temperature of at -least 150 F. Vand withthe hydrocarbon in the liquid phase.

16.. The method according to claim 15 par a..-

18. The method according -11o-.claim 15 whrein the polymerizing agent issulphuric aci 19. The method according to, claim l15 .15- bon with from0.1% to 0.5%

wherein vthe separation of the hydrocarbon from the. impurities andreaction products is effected by ldistillation. f

l 20. The method according toJ claim wherein two oxides are employedconsisting Aof oxides of copper and iron.

#21.The method according to claim 15 20- complishing polymerization ofremaini gum-forming constituents and distilling the drocarbon from thereaction products.` 24. The method of refining light hydrocarbonscomprising treating the hydrocar- 23 bon with from 0.1% to 0.5% ofstrong sulcarbon reaction products resulting :trom said ac id treatment,with a hard, porous gel in a m. quantity insufficient to adsorb thereaction products, said latter. treatment accomplishing polymerizationof remaining gum-form-- lng constituents and then separating thehydrocarbon from the reaction products.

25. The method according to claim. 2d wherein the separation from thereaction products is edected by distillation.

26. rlhe method according to yclaim 24 wherein the treatment with thegel is etiected an at an elevated temperature and with the hydrocarbonin the liquid phase.

27..'lhe process of refining hydrocarbons containing unsaturatedconstituents comprising treating the hydrocarbon with a suit- 45 ablereagent in an amount suihcient to polymerize a portion only of gumforming constitnents in said hydrocarbon,- then contacting saidhydrocarbon :with la porous, adsorbentrnaterial in an insucient quantityto sa adsorb any substantial amount of the polynier-ized gums in saidhydrocarbon, said latzter treatment accomplishing polymerization ofremaining gum forming constituents and iinally separating the purifiedhydrocarbon E5 V trom the impurities.

28. The process in accordance with claim 27 wherein said absorbenttreatment is eii'ected at an elevated temperature and with saidhydrocarbon in the liquid phase. Y ca 29. The method according. to claim27 wherein the treatment of the hydrocarbon,

with the initial polymerizing agent is edec'ted in stages.

30. The method of refining light hydrocar- YVM bons comprising treatingthe hydrocarbon phurio acid, contacting the treated hydrocaron whilecontamina in solution acid-hydrowith a small quantity of acid, thentreating the vhydrocarbon containing in solution acidhydrocarbonreaction products resultingfrom said acid treatment, with av porous,-adsorbent material, said latter treatment accomplishing polymerizationof remaining gum-forming constituents and-then separating the purifiedhydrocarbon from the impurities and resulting reaction products.

31. The process in accordance with claim 30 wherein 'said lighthydrocarbons are of the nature of cracked benzol.

32. The process in accordance with claim 30 wherein said acid isstrongsulphuric acid in a quantity of from 0.1% to 0.5% by weight of thehydrocarbon.

33. The process in'accordance with claim gasoline, kerosene and '34. Theprocess in accordance Withclaim 30 wherein the adsorbent is used in ayproportion of one part to more than parts of hydrocarbon.

35.".lhe process in accordance with claim wherein the treatment of thehydrocarbon with the adsorbent is ele'cted at an elevated temperatureand with the hydrocarbon in the liquid phase.` l

.36. 'lhe process in accordance with claim 30 wherein the treatmentofthe hydrocarbon with the adsorbent is edeote'd by passing thevhydrocarbon through a bed of the adsorbent.

37. 'lhe process in accordance with claim 30 wherein the `hydrocarbonafter treat-ment with the adsorbentis separated from impurities thereinby distillation. y

38. rlhe process in accordance with claim 30 wherein the hydrocarbonafter treatment with the adsorbent is separated from impurities thereinby treatment-with a porous adsorbent material at vnormal temperature andpressure. 1

39. rlhe process in accordance with claim 30 wherein sludge formed bysaid acid treatnient is removed prior to the adsorbent treatnient. g

40. rlhe process in accordance with claim 30 wherein the adsorbent isremoved from the hydrocarbon prior to theseparationfof the reactionproducts and other impurities.

al. 'lhe process in accordance with claim 30 wherein said adsorbent hasassociated vtherewith at least one metallic oxide capable oit readilycombining with sulphur,

42. The process of refining liquid hydrocarbons of the nature ot crackedgasoline,

kerosene, benzol, and the like, comprising treating the hydrocarbon withacid in a quantity sufiicient to polymerize a portion only oiigum-forming constituents contained' in said hydrocarbon, contacting thetreated hydrocarbon while containing in solution acidhydrocarbonreaction products resulting from said acid treatment, with a porous,

30 wherein said adsorbent is a hard, porous adsorbent material at anelevated temperature, whereby additional reaction vproducts forni insaid hydrocarbon, and separating the hydrocarbon from the reactionproducts.

43. The process of refining light hydrocarbons comprising, contacting anacidulated light hydrocarbon containing gums and gumforming constituentswith a porous adsorbent material in a quantity insulicient toremove anysubstantial amount of reaction products polymerization .of remaininggum-forming constituents and separating the hydrocarbon from theimpurities remaining therein.

44. The process in accordance with claim 43 wherein the contact of thehydrocarbon and adsorbent is eected at an elevated temperature and withthe hydrocarbon in the liquid phase.

45. The process in accordance with claim. 43 wherein the contact ofhydrocarbon and adsorbent is effected at a temperature suficientlyhighto melt any elemental sulphur in said hydrocarbon. 46. The method ofrefining liquid hydrocarbons'which comprises'treating the hydro carboncontaining element sulphur with a hard, porousv gel material havingpores of such size that it will adsorb water vapor to such an extent asto contain not less than about 1( of its own weight of water when inequilibrium with water vapor at C. and a partial pressure ofsubstantially 22 mm. of mercury, the treatment beingelected at atemperature of about E-300 F. and with the hydrocarbon liquid.

47. .Thamethod according to claim 46 wherein the gel material is silicagel.

48. The method according to claim 46 wherein the ratio of liquid treatedto the material is more than 25-t0 1.

Aif)

in solution, said treatment accomplishing Yso as to include a metallicoxide, the treatment being effected at an elevated temperature, saidoxide having an affinity for sulphur and its sulphur compound beingreconvertible into the oxide-by heating under oxidizing conditions.

52. The method oi reining liquid hydrocarbons which comprises treatingthe hquid with silica gel having at least one metallic oxide associatedtherewith at an elevated temperature and under pressure suicient to keepthe hydrocarbon in the liquid phase said oxide having an allinity forsulphur an its sulphur compound being reconvertible into the oxide byheating conditions, one said metallic oxide being copper oxide.

In testimony whereof we hereunto aix our signatures.

ERNEST B. MILLER. GERALD C. CONNOLLY.

49. The method of refining liquid hydra carbons which comprises treatingthe with/a hard porous silica gel imprenated so as to include copperoxide, which oxide is present in a' ,maximum amount of about 1% of theweight. of the dry gel, the treatment being effected ata`temperatuie`above 240 F. but below the cracking tem erature of thehydrocarbon, and under s cient -pressure tql maintain thehydrocarbon inthe liquid ase.

30. The method of refining liquid hydroA carbons which comprisestreating the liquid 1 with a hard, porous, silica gel having at leastone metallic oxide associated therewith at an elevated temperature andunder pressure suficient to keep the hydrocarbon in the liquid phase,said oxide having an aiinity for su1- phur and its sulphur compoundbeing-reconvertible into the'oxide by'heating under oxidizingconditions.

51. The method carbons which comprises treating the liquid 65 with ahard,`porous silica gel impregnated of refining liquid hydro-l underoxidizing 80

